|Numéro de publication||US7655582 B2|
|Type de publication||Octroi|
|Numéro de demande||US 10/844,640|
|Date de publication||2 févr. 2010|
|Date de dépôt||12 mai 2004|
|Date de priorité||12 mai 2004|
|État de paiement des frais||Payé|
|Autre référence de publication||CA2563984A1, CA2563984C, EP1745101A1, US20050255777, WO2005113674A1|
|Numéro de publication||10844640, 844640, US 7655582 B2, US 7655582B2, US-B2-7655582, US7655582 B2, US7655582B2|
|Inventeurs||Kimberly M. McLoughlin, Sehyun Kim|
|Cessionnaire d'origine||Sunoco Chemicals, Inc.|
|Exporter la citation||BiBTeX, EndNote, RefMan|
|Citations de brevets (19), Référencé par (4), Classifications (25), Événements juridiques (5)|
|Liens externes: USPTO, Cession USPTO, Espacenet|
The present invention is related to the field of polypropylene compositions for use in the production of fibers and non-woven fabrics. More particularly, the present invention is related to the field of polypropylene blends containing ethylene that are useful in the production of fibers and non-woven fabrics.
In the production of non-woven fabrics, such as spunbond and meltblown fabrics, molten polymer is extruded through a many holed die, or spinneret. The fibers are drawn by an air current and then collected in a random array to form a web of fibers. The web thus formed is then bonded by heating it to soften the polymer fibers and then passing the web through smooth or engraved calender rollers to bond the fibers. Bonding improves the strength of the non-woven fabric over non-bonded materials.
In many cases, the bonding process governs the speed at which a producer can run a line producing non-woven fabrics. The time that the web requires between the nips in the calendering process is controlled by the properties of the polymer in the fibers that make up the web, as well as the temperature and pressure of the calender rolls.
In certain applications it is desirable to combine one or more webs of non-woven fabric. Typical constructions of this type combine one or more webs of spunbond fabric with a web of meltblown fabric. Such constructions are termed spunbond-meltblown (S-M) and spunbond-meltblown-spunbond (S-M-S) fabrics. A problem arises in the bonding process for such constructions stemming from the relatively high temperatures needed to bond the spunbond material. These temperatures may cause partial melting of the much finer fibers that make up the meltblown web, resulting in pinholes which compromise the barrier properties of the fabric.
It is known that a PP having a high level of solubles can improve process performance in non-woven fabrics, providing lower bonding temperatures and a wider bonding window. It is, however, a burden to PP manufacturers to produce high solubles because large amounts of unwanted wide-spec materials are generated to reach targeted high solubles. Also, it is known that the solubles are responsible for smoke generation during fiber spinning.
It would therefore be desirable to provide a polypropylene material that provides the wide bonding window and low bonding temperatures of a high solubles material without the drawbacks of large amounts of off-spec material and increased smoke generation in processing.
The present invention provides novel polypropylene blends for use in fiber and non-woven fabric production. The polypropylene blends according to the current invention comprise from about 80 to about 95 percent by weight of a propylene homopolymer having a decalin solubles content of about 4 percent by weight or less, preferably from 2 percent by weight to about 4 percent by weight, and from about 5 to about 20 percent by weight of an ethylene/propylene random copolymer. The polypropylene blends have a total ethylene content of about 1 percent by weight or less, and a decalin solubles content of about 6 percent by weight or less.
The ethylene/propylene random copolymers used in the polypropylene blends according to the current invention preferably have an ethylene content of about 7 percent by weight or less.
Blending of the propylene homopolymer and ethylene/propylene random copolymer can be accomplished either by in-reactor blending, using sequential polymerization reactors, or by mechanical blending of materials in an extruder.
The polypropylene blends according to the current invention preferably have a melt flow index (MFI), measured in dg/min at 230° C., which is suitable for spunbond fiber processing. Material having the appropriate melt flow index for spunbond processing can be produced either in-reactor by known techniques, or by controlled degradation of a low melt flow index material according to the current invention.
The polypropylene blends according to the current invention are suitable for use in spunbond, and combination spunbond-meltblown non-woven fabrics. Particularly, the polypropylene blends according to the current invention are useful in multilayer fabrics such as spunbond-meltblown (S-M), and spunbond-meltblown-spunbond (S-M-S) constructions.
It has been found that the incorporation of minor amounts of ethylene in a spunbond fabric allows for bonding of the fibers at lower calender temperatures without significantly compromising the strength of the resulting fabric. The inventors postulate that alternatively, higher line speeds may be obtained at a given temperature and pressure, allowing producers to achieve higher throughput on equipment without compromising fabric strength. Further, the bonding window obtained with materials having minor amounts of ethylene incorporated according to the current invention is comparable to that obtained with standard propylene homopolymers used in fiber production.
Achieving lower bonding temperatures is important in making fabric constructions that contain both spunbond and meltblown webs, such as S-M-S constructions for medical and hygiene applications. Bonding those types of constructions requires calender heating that effectively bonds the spunbond fabric without overheating the meltblown web, since overheating causes voids that destroy the barrier properties of the meltblown web. Reducing the calender temperature needed for the spunbond web can help processors to achieve this balance.
It has been found that introduction of about 1 percent or less by weight of ethylene via blending of an ethylene/propylene random copolymer with a propylene homopolymer provides the best fabric strength at a given calendering temperature. Accordingly, the polypropylene blends according to the current invention comprise from about 80 to about 95 percent by weight of a propylene homopolymer and from about 5 to about 20 percent by weight of an ethylene/propylene random copolymer.
The propylene homopolymers used in the blends according to the current invention have a decalin soluble content of about 4 percent by weight or less, preferably from 2 percent by weight to about 4 percent by weight. The polypropylene blends according to the current invention have a total decalin solubles content of about 6 percent by weight or less. Incorporation of an ethylene/propylene random copolymer into polypropylene for spunbond and meltblown fabrics allows resin manufacturers to avoid the problems associated with producing high solubles content polypropylene for fiber processing.
The ethylene/propylene random copolymers used in the blends according to the current invention have an ethylene content of about 7 percent by weight or less, preferably from about 2 to about 3 percent by weight. The polypropylene blends according to the current invention have a total ethylene content of about 1 percent by weight or less, preferably about 0.5 percent by weight or less.
The polypropylene blends according to the current invention preferably have a melt flow index (MFI), measured in dg/min at 230° C. that is suitable for spunbond fiber processing. Suitable melt flow indices for spunbond fiber processing range from about 8 dg/min to about 55 dg/min. Polypropylene blends according to the current invention having a suitable melt flow index for spunbond fiber processing can be obtained by using known methods to produce a reactor material of the proper melt flow index. Alternatively, a low melt flow index material according to the current invention may be produced and then adjusted using controlled rheology techniques to produce a final material having a melt flow index suitable for spunbond processing. Further, it will be recognized that controlled rheology materials may be pelletized for shipment to processors, or the controlled rheology treatment may be completed by a processor directly prior to fiber production. It will be recognized by those of ordinary skill in the art that the present invention is not limited to a particular melt flow index range or means of achieving a particular melt flow index.
Samples of polypropylenes for production of spunbond fabrics were produced by extruding each of the powder samples described in Table I with 1000 ppm Irganox 1076 m, 500 ppm Irgafos 168, 300 ppm calcium stearate, and sufficient Trigonox 101 peroxide to yield a pellet MFI of approximately 25 dg/min. Two 0.5% ethylene blends (2 and 12 initial MFI) were produced by dry-blending a 2.5% ethylene content random copolymer (RCP) with a propylene homopolymer (HPP) powder prior to extruding with peroxide and additives. Another 0.5% ethylene blend was produced by dry-blending a 3.5% ethylene random copolymer with the same propylene homopolymer powder prior to extruding with peroxide and additives. Also tested were a polypropylene homopolymer, a 0.5% ethylene mini-random copolymer (mRCP), and a 2.5% ethylene random copolymer.
Resins used for Random Copolymer Spunbond Studies
Fabrics were produced on a ST&CC Reifenhauser Reicofil II spunbond line using a 2734 hole, 0.6 mm capillary diameter spinneret. Extruder and die temperatures were set to achieve a nominal melt temperature of 235° C. The target throughput was 0.65 ghm. Suction and cooling fans speeds were held at 2200 and 1700 rpm, respectively, to achieve a target denier of about 2.9 g/9000 m. Bond curves were measured for 30 gsm fabric samples collected at a series of calender roll temperatures. The calender temperatures were selected based on the ethylene content of the resin, as shown in Table II. (As usual, the smooth calender roll was set 5° C. cooler than the engraved roll.)
Calender Temperature Settings
As shown in Table III, filament diameters are very consistent among all fabrics produced here, as measured by microscope observation of fabrics. Since fan speeds were held constant, this result indicates that neither ethylene content nor initial powder MFI significantly affected the resistance to draw force for this set of polymers. These results suggest that a mini-random copolymer or HPP/RCP blend containing a standard spunbond additive package could be processed using with the same spinning conditions that would be used for a HPP of the same MFI.
Filament Deniers Measured on Spunbond Fabrics
Bond curves for the materials cracked from 2-MFI powders are shown in
Bond curves for the grades cracked from 12-MFI powders are shown in
The bonding windows of the RCP/HPP blends are somewhat broader than the bonding window of the mRCP and somewhat narrower than the bonding window of the HPP. Bonding window is defined here as the range of calender temperatures over which the HPP control exhibits tensile strength at least 90% as high as the maximum. For the results reported in
Bond Temp Range (° C.)
Width (° C.)
0.5% blend with 2.5% RCP
0.5% blend with 3.5% RCP
As shown in
It has also been found that incorporation of ethylene according to the current invention does not adversely impact fabric elongation. In fact, as shown in
As shown in
It has thus been shown that polypropylene blends produced according to the current invention can be used in the production of non-woven fabrics at standard conditions without compromising the strength of the fabric produced compared to standard propylene homopolymers. This allows manufacturers to obtain the same performance obtained with propylene homopolymers without the problems inherent in producing high solubles homopolymers and the smoke generation associated with fiber production using high solubles materials.
It will also be appreciated that the properties of the polypropylene blends according to the current invention will allow the use of lower processing temperatures. Alternatively, it may be possible for manufacturers to use higher line speeds on a non-woven processing line at a given temperature without compromising fabric strength, thus allowing producer to achieve higher throughput on a given line.
The use of lower processing temperatures is a benefit in the production of multilayer S-M and S-M-S constructions where preserving the barrier properties of the meltblown web in the construction is important.
Thus some of the benefits of the instant invention have been outlined broadly. However, additional benefits of the current invention will be apparent to those having skill in the art. The full scope of the invention will be understood by the appended claims.
|Brevet cité||Date de dépôt||Date de publication||Déposant||Titre|
|US5331054 *||19 oct. 1992||19 juil. 1994||Mitsubishi Petrochemical Company, Ltd.||Propylene copolymer composition|
|US5460884 *||25 août 1994||24 oct. 1995||Kimberly-Clark Corporation||Soft and strong thermoplastic polymer fibers and nonwoven fabric made therefrom|
|US5691043||25 avr. 1995||25 nov. 1997||Mobil Oil Corporation||Uniaxially shrinkable biaxially oriented polypropylene film and its method of preparation|
|US5726103||12 déc. 1996||10 mars 1998||Exxon Chemical Co.||Fibers and fabrics incorporating lower melting propylene polymers|
|US5763080||12 déc. 1996||9 juin 1998||Exxon Chemical Co.||Fibers and fabrics incorporating lower melting propylene polymers|
|US6225411||19 avr. 1999||1 mai 2001||Montell Technology Company Bv||Soft propylene polymer blend with high melt strength|
|US6248833||29 févr. 2000||19 juin 2001||Exxon Mobil Chemical Patents Inc.||Fibers and fabrics prepared with propylene impact copolymers|
|US6309736||25 juin 1997||30 oct. 2001||Kimberly-Clark Worldwide, Inc.||Low gauge films and film/nonwoven laminates|
|US6346580||15 sept. 2000||12 févr. 2002||Sumitomo Chemical Co., Ltd.||Thermoplastic resin composition|
|US6437048 *||2 déc. 1996||20 août 2002||Chisso Corporation||Molded resin articles|
|US6444774||29 sept. 1998||3 sept. 2002||Exxonmobil Chemical Patents, Inc.||Propylene polymers for fibers and fabrics|
|US6639018||25 févr. 2002||28 oct. 2003||Sumitomo Chemical Company, Limited||Polypropylene resin composition and process for producing the same|
|US20030088022||20 juin 2002||8 mai 2003||Lin Chon Y.||Polypropylene compositions methods of making the same|
|US20030176611||5 nov. 2002||18 sept. 2003||Stevens James C.||Isotactic propylene copolymer fibers, their preparation and use|
|US20040041299||27 août 2002||4 mars 2004||Sehyun Kim||Resin compositions for producing biaxially oriented polypropylene films|
|EP0482918A2||23 oct. 1991||29 avr. 1992||Amoco Corporation||Self-bonded nonwoven web and net-like web composites|
|EP0812371A1||9 févr. 1996||17 déc. 1997||Kimberly-Clark Worldwide, Inc.||Nonwoven fabric from polymers containing particular types of copolymers and having an aesthetically pleasing hand|
|WO2004029341A1||23 sept. 2003||8 avr. 2004||Basell Poliolefine Spa||Polypropylene fibres suitable for thermally bonded non-woven fabrics|
|WO2004029342A1||23 sept. 2003||8 avr. 2004||Basell Poliolefine Spa||Polypropylene fibres suitable for spunbonded non-woven fabrics|
|Brevet citant||Date de dépôt||Date de publication||Déposant||Titre|
|US8399587 *||20 déc. 2009||19 mars 2013||Fina Technology, Inc.||Mini-random copolymer resins having improved mechanical toughness and related properties suitable for thin wall thermoforming applications|
|US8466235 *||10 mai 2010||18 juin 2013||Braskem America, Inc.||Polypropylene blends for non-woven production|
|US20100160533 *||20 déc. 2009||24 juin 2010||Fine Technology, Inc.||Mini-Random Copolymer Resins having Improved Mechanical toughness and Related Properties Suitable for Thin Wall Thermoforming Applications|
|US20110021708 *||27 janv. 2011||Sehyun Kim||Polypropylene blends for non-woven production|
|Classification aux États-Unis||442/381, 442/327, 442/401, 442/382, 442/400, 428/373|
|Classification internationale||C08L23/14, D04H3/16, B32B5/26, D04H1/00, C08L23/12, D04H1/56, D04H3/00|
|Classification coopérative||Y10T442/681, Y10T442/60, Y10T442/659, Y10T442/68, Y10T442/66, Y10T442/69, C08L23/12, Y10T428/2929, C08L23/14, C08L2205/02|
|Classification européenne||C08L23/14, C08L23/12|
|12 mai 2006||AS||Assignment|
Owner name: SUNOCO, INC. (R&M),PENNSYLVANIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MCLOUGHLIN, KIMBERLY M.;KIM, SEHYUN;SIGNING DATES FROM 20060501 TO 20060503;REEL/FRAME:017879/0931
|19 nov. 2009||AS||Assignment|
Owner name: SUNOCO CHEMICALS, INC.,PENNSYLVANIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:SUNOCO, INC. (R&M);REEL/FRAME:023544/0271
Effective date: 20090101
|17 nov. 2010||AS||Assignment|
Owner name: BRASKEM PP AMERICAS, INC., PENNSYLVANIA
Free format text: CHANGE OF NAME;ASSIGNOR:SUNOCO CHEMICALS, INC.;REEL/FRAME:025379/0895
Effective date: 20100401
Owner name: SUNOCO CHEMICALS, INC., PENNSYLVANIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:SUNOCO, INC. (R&M);REEL/FRAME:025379/0866
Effective date: 20090101
|10 janv. 2011||AS||Assignment|
Owner name: BRASKEM AMERICA, INC., PENNSYLVANIA
Free format text: MERGER;ASSIGNOR:BRASKEM PP AMERICAS, INC.;REEL/FRAME:025604/0572
Effective date: 20110101
|3 juil. 2013||FPAY||Fee payment|
Year of fee payment: 4